当前位置:科学网首页 > 小柯机器人 >详情
CPET介质的电催化金属氢化物生成
作者:小柯机器人 发布时间:2022/7/24 19:50:18

瑞士苏黎世联邦理工学院Mougel, Victor团队报道了CPET介质的电催化金属氢化物生成。相关研究成果于2022年7月20日发表在国际顶尖学术期刊《自然》。

过渡金属氢化物(M-H)是广泛酶促过程和催化反应中普遍存在的中间体,在H+/H2相互转化、CO2还原为甲酸(HCOOH)和氢化反应中发挥着核心作用。M-H的容易形成是进一步提高这些反应能量效率的关键挑战。具体来说,使用温和的质子源轻松电化学生成M-H是实现高选择性的关键,而不是在CO2电还原为HCOOH的过程中形成竞争性CO和H2,HCOOH是附加值最高的CO2还原产物。

该文中,研究人员介绍了一种使用协同质子-电子转移(CPET)介质的电催化M-H生成策略。作为原理证明,研究了一系列CPET介体与CO2电还原催化剂[MnI(bpy)(CO)3Br](bpy=2,2′-联吡啶)的组合,探讨了产物选择性从CO到HCOOH的反转,以评估氢化锰(Mn-H)生成步骤的效率。通过原位光谱技术证明了Mn-H物种的形成,并确定了该机制发生的热力学边界条件。合成的铁硫簇被认为是该系统的最佳氯化聚乙烯介体,能够制备生成羟基乙酸的基准催化系统。

附:英文原文

Title: Electrocatalytic metal hydride generation using CPET mediators

Author: Dey, Subal, Masero, Fabio, Brack, Enzo, Fontecave, Marc, Mougel, Victor

Issue&Volume: 2022-07-20

Abstract: Transition metal hydrides (M-H) are ubiquitous intermediates in a wide range of enzymatic processes and catalytic reactions, playing a central role in H+/H2 interconversion1, the reduction of CO2 to formic acid (HCOOH)2 and in hydrogenation reactions. The facile formation of M-H is a critical challenge to address to further improve the energy efficiency of these reactions. Specifically, the easy electrochemical generation of M-H using mild proton sources is key to enable high selectivity versus competitive CO and H2 formation in the CO2 electroreduction to HCOOH, the highest value-added CO2 reduction product3. Here we introduce a strategy for electrocatalytic M-H generation using concerted proton–electron transfer (CPET) mediators. As a proof of principle, the combination of a series of CPET mediators with the CO2 electroreduction catalyst [MnI(bpy)(CO)3Br] (bpy=2,2′-bipyridine) was investigated, probing the reversal of the product selectivity from CO to HCOOH to evaluate the efficiency of the manganese hydride (Mn-H) generation step. We demonstrate the formation of the Mn-H species by in situ spectroscopic techniques and determine the thermodynamic boundary conditions for this mechanism to occur. A synthetic iron–sulfur cluster is identified as the best CPET mediator for the system, enabling the preparation of a benchmark catalytic system for HCOOH generation.

DOI: 10.1038/s41586-022-04874-z

Source: https://www.nature.com/articles/s41586-022-04874-z

期刊信息

Nature:《自然》,创刊于1869年。隶属于施普林格·自然出版集团,最新IF:42.778
官方网址:http://www.nature.com/